US4148983A - Polymerization and copolymerization of trans-piperylene and isoprene - Google Patents

Polymerization and copolymerization of trans-piperylene and isoprene Download PDF

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Publication number
US4148983A
US4148983A US05/893,725 US89372578A US4148983A US 4148983 A US4148983 A US 4148983A US 89372578 A US89372578 A US 89372578A US 4148983 A US4148983 A US 4148983A
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chromium
phosphite
compound
group
process according
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US05/893,725
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Morford C. Throckmorton
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Goodyear Tire and Rubber Co
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Goodyear Tire and Rubber Co
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Priority to US05/893,725 priority Critical patent/US4148983A/en
Priority to CA000322362A priority patent/CA1120911A/fr
Priority to GB7907994A priority patent/GB2018782B/en
Priority to DE19792911307 priority patent/DE2911307A1/de
Priority to FR7908264A priority patent/FR2421916A1/fr
Priority to IT48570/79A priority patent/IT1116536B/it
Priority to BR7902011A priority patent/BR7902011A/pt
Priority to NL7902612A priority patent/NL7902612A/xx
Priority to JP4086579A priority patent/JPS54135884A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • This invention is directed to a method of polymerization and/or copolymerization of diolefins selected from the group of monomers consisting of trans-1,3-pentadiene and isoprene. It is also directed to catalyst systems used in these polymerizations.
  • the products of these polymerizations have properties ranging from rubbers to plastics and thereby find utility in the preparation of vulcanized rubber products and plastics.
  • the polymers which have glass transition temperatures (Tg's) which are relatively low may be utilized in tire carcass stocks while those with high Tg's may be used in tread stocks.
  • this invention is directed to the use of a tertiary catalyst system comprising (A) an organometallic compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylmagnesiums, and dialkylzincs, (B) a soluble chromium compound selected from the group consisting of chromium salts of organic acids containing from 2 to 20 carbon atoms, organic complex compounds of chromium containing tridentate organic ligands, and ⁇ -bonded organochromium compounds, and (C) a member selected from tris(2-chloroethyl)phosphite, dialkyl hydrogen phosphites and diaryl hydrogen phosphites, to polymerize and copolymerize diolefins selected from the group of trans-1,3-pentadiene and isoprene.
  • A an organometallic compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydr
  • Italian Patent No. 538,453 and British Patent No. 835,752 indicate that a binary catalyst system of chromium acetylacetonate and triethylaluminum polymerizes butadiene to a prevailingly 1,2-enchained linear polybutadiene and isoprene to prevailingly 3,4-polyisoprene.
  • Polyisoprenes prepared with a binary catalyst system such as chromium acetylacetonate plus triethylaluminum or tris( ⁇ -allyl)chromium plus a Lewis acid were generally low molecular weight liquids which had intrinsic viscosities of about 0.2 dl/g. This is reported in J. Polym. Sci., Chem. Ed 11, 2489 (1973).
  • Chem. Abs. 80, 109590 v (1974) reports the preparation of 1,2-polybutadiene by polymerizing butadiene in the presence of hydrogen using chromium acetylacetonate, dibutylphosphonate and triisobutylaluminum.
  • Chem. Abs. 80, 4644 n. (1974) reports that a polymer analyzing 95 percent 1,2-polybutadiene was prepared using a chromium compound, an organoaluminum compound and phosphoric acid ester catalyst system.
  • the invention consists of the polymerization and copolymerization of at least one diolefin selected from the group consisting of trans-1,3-pentadiene and isoprene employing as a catalyst a mixture of (A) at least one organometallic compound selected from the group consisting of aluminum trialkyls, magnesium dialkyls and zinc dialkyls, (B) at least one soluble chromium compound selected from the group consisting of chromium salts of organic acids containing from 2 to 20 carbon atoms, organic complex compounds of chromium containing tridentate ligands and ⁇ -bonded organo chromium compounds and (C) at least one member selected from tris(2-chloroethyl)phosphite, dialkyl hydrogen phosphites and diaryl hydrogen phosphites.
  • the soluble chromium compounds employed in the practice of this invention may be chromium salts of carboxylic acids containing from 2 to 20 carbon atoms.
  • the organic complex compounds of chromium containing tridentate organic ligands are also suitable. Tridentate organic ligands have three positions to which a covalent or coordinate bond with the metal may be formed. Representative of such a chromium containing tridentate compound is chromium acetylacetonate.
  • the ⁇ -bonded organochromium compounds may be represented by tris(allyl)chromium, tris(methylallyl)chromium, tris(crotyl)chromium, ⁇ -cyclopentadiene chromium tricarbonyl and ⁇ -phenyl chromium tricarbonyl.
  • the preferred soluble chromium compounds useful in this invention are the chromium salts of organic acids and may be represented by chromium octanoate, chromium benzoate, chromium neo-decanoate, chromium benzoate, chromium neo-decanoate, chromium naphthenate, chromium oxalate and chromium stearate.
  • the most preferred are chromium naphthenate, chromium neo-decanoate, and chromium octanoate.
  • the organometallic compounds employed in this invention are aluminum trialkyls or dialkylaluminum hydrides, representative examples of which are aluminum trimethyl, aluminum triethyl, aluminum tri-n-propyl, aluminum tri-n-butyl, aluminum triisobutyl, aluminum tripentyl, aluminum trihexyl, aluminum trioctyl, diethyl-aluminum hydride and diisobutylaluminum hydride and the like.
  • dialkyl magnesium compounds useful in this invention may be represented by di-n-hexylmagnesium and n-butylethylmagnesium and the like.
  • the dialkyl zinc compounds may be represented by diethylzinc and dibutylzinc and the like.
  • the dialkyl hydrogen phosphites may be represented by the tautomeric structures: ##STR1## where R and R' indicate alkyl groups which may or may not be identical.
  • the dialkyl phosphites exist substantially in the keto form (shown on the left) and are associated in dimeric or trimeric groupings by hydrogen bonding.
  • the nomenclature dialkyl hydrogen phosphite if applied strictly, describes only the keto tautomer, but it commonly is applied to both tautomeric forms and that it is the intent herein.
  • the phosphites of this invention may be described further as having at least one phosphinic hydrogen atom.
  • dialkyl hydrogen phosphites useful in the preparation of the catalyst of this invention are those containing from 1 to 20 carbon atoms in the alkyl groups. They may be represented by dimethyl hydrogen phosphite, diethyl hydrogen phosphite, diisopropyl hydrogen phosphite, dibutyl hydrogen phosphite, bis(2-ethylhexyl)hydrogen phosphite or dioctyl hydrogen phosphite, didodecyl hydrogen phosphite, dioctadecyl hydrogen phosphite, ethyl butyl hydrogen phosphite, methyl hexyl hydrogen phosphite and the like.
  • Diaryl hydrogen phosphites containing from 6 to 12 carbon atoms in the aryl groups may also be employed in the practice of this invention. They may be represented by dibenzyl hydrogen phosphite and diphenyl hydrogen phosphite. Cycloalkyl hydrogen phosphites, such as dicyclohexyl hydrogen phosphite, also may be used; and a monoalkyl-, monoaryl hydrogen phosphite, such as ethyl phenyl hydrogen phosphite and butyl benzyl hydrogen phosphite may also be utilized.
  • Tris(2-chloroethyl)phosphite is also useful in the invention.
  • dialkyl hydrogen phosphites containing from 1 to 8 carbon atoms per alkyl group are the preferred phosphite containing compounds.
  • the catalyst system of the present invention has polymerization activity over a wide range of total catalyst concentration and catalyst component ratios. Catalyst components apparently interreact to form the active catalyst species. As a result, the optimum concentration for any one catalyst component is dependent upon the concentrations of the other catalyst components. While polymerizations will occur over a wide range of catalyst concentrations and ratios, the polymers having the most desirable properties are obtained within a narrower mole ratios range.
  • the molar ratio of the organometallic compound to the chromium compound can be varied from about 20/1 to about 2/1. However, a more preferred range of Me/Cr is from about 8/1 to about 4/1.
  • the molar ratio of the tris(2-chloroethyl)phosphite, dialkyl or diaryl hydrogen phosphite to chromium compound (P/Cr) may be varied from about 0.2/1 to about 10/1, with a more preferred range of P/Cr being from about 0.5/1 to about 3/1.
  • Catalyst components may be charged to the polymerization system as separate catalyst components in either a step-wise or simultaneous manner, usually called the in situ preparation.
  • the catalyst components may also be preformed by premixing the three components outside of the polymerization system. The resulting premixed catalyst components then may be added to the polymerization systems.
  • the amount of total catalyst employed depends on such factors as purity of the components, polymerization rate desired, and the temperature. Therefore, specific total concentrations of catalyst cannot be set forth except to say that catalytic amounts should be employed.
  • Successful polymerizations have been made using molar ratios of monomer to the chromium component in the ternary catalyst system ranging between about 300/1 to about 4,000/1.
  • the preferred monomer to chromium concentration generally is between 600/1 and 2,000/1.
  • the polymerizations of this invention are carried out in inert solvent systems and are, thus, considered to be solution polymerizations.
  • inert solvent the solvent or diluent employed does not enter into the polymer structure nor does it have an adverse effect on the catalyst activity.
  • solvents are usually aliphatic, aromatic or cycloaliphatic hydrocarbons.
  • the preferred solvents are hexane, pentane, benzene, toluene and cyclohexane.
  • the solvent/monomer volume ratio may be varied over a wide range. Up to 20 or more/1 volume ratio of solvent to monomer may be employed. It is usually preferred to employ a solvent/monomer volume ratio of about 3/1 to about 6/1. It is possible to employ a suspension polymerization system in the practice of this invention. This may be done by choosing a solvent or diluent in which the polymer formed is insoluble.
  • Temperatures employed in the practice of this invention are not critical and may vary widely from a low temperature, for example, such as -10° C. or below to a high temperature of 100° C. or above. However, it is usually desirable to employ a more convenient temperature between about 20° C. and about 90° C.
  • the practice of the invention is further illustrated by reference to the following examples which are intended to be representative rather than restrictive of the scope of the invention. Unless otherwise noted, all parts and percentages are by weight.
  • the dilute solution viscosities (DSV) which are reported in deciliters per gram were determined in toluene at 30° C.
  • the glass transition temperatures (Tg) were determined using Du Pont's model 900 Differential Thermal Analyzer (DTA).
  • DTA Differential Thermal Analyzer
  • the microstructures of the polypiperylenes were determined by a combination of Nuclear Magnetic Resonance (NMR), using a Varian A-60 spectrometer, and Infrared (IR) techniques, as described by D. H. Beebe, et al, in J. Polym. Sci., Part A-1 (in press).
  • the microstructures of other polymers were determined by either NMR or IR methods.
  • a premix containing a solution of transpiperylene in hexane at a concentration of 10 grams of monomer per hundred milliliters of total solution was charged to a series of 4-oz bottles.
  • the catalyst components were charged by the in situ addition technique in the following order: The organometallic compound was charged first, followed by the chromium compound, followed by a dialkyl phosphite compound.
  • the specific catalyst compounds in millimoles per hundred grams of monomer (mhm) are identified in Table 1 below.
  • the bottles were placed in a water bath and maintained at 50° C. and tumbled end-over-end to provide agitation. The polymerizations were terminated by the addition of one milliliter of methanol plus one part/100 g.
  • Example 2 The procedure in this example was similar to that in Example I except that chromium salts of different carboxylic acids and chromium acetylacetonate were utilized as the chromium catalyst component. Results are shown in Table 2.
  • Example III The procedure in this example was similar to that utilized in Example I except that different organoaluminum compounds were used, and in one instance, no phosphite compound was added in order to illustrate its importance to produce solid, moderately high cis-1,4-polypiperylene elastomers. Results are presented in Table III.
  • Example 5 The procedure used in this example was similar to that in Example I except that either two or all three of the catalyst components were premixed instead of adding them "in situ" to the piperylene in hexane solution.
  • a solution of 4,270 grams of this distillate in 11,730 g of industrial grade hexane was passed through a silica gel column, and charged into a ten-gallon stirred reactor. Nitrogen was bubbled through the solution for two minutes and vented to remove any dissolved air. The temperature of the premix was raised to 50° C.
  • a sample of polymer cement was withdrawn from the reactor after one hour, and it had a solids content of 9.8 wt %, indicating about 54 percent conversion. After three hours, the solids content was 10.8 percent.
  • the polymerization was terminated by adding 100 ml of a 34 percent aqueous solution of a 90 percent solution of tetrasodium salt of ethylenediaminetetraacetic acid and 23 grams of dibutyl-para-cresol dissolved in 400 mls benzene and 100 mls of methanol.
  • the polymer cement was dried in trays at 40° C. under vacuum, and 1786 grams of dry polymer were recovered.
  • the microstructure of the polymer was 75 percent cis-1,4-, 21 percent trans-1,2- and 4 percent 3,4-polypiperylene. Its Mooney viscosity (ML-4 at 212° F.) was 63 and its DSV was 2.8 dl/g. The Tg was -44° C.
  • a purified solution of trans-piperylene in n-pentane containing 10 g of piperylene per 100 ml of solution was prepared.
  • a second purified solution in pentane containing 10 g of isoprene per 100 ml of solution also was prepared. Aliquots of these solutions were measured into a series of 4-ounce bottles to prepare premixes containing a total of 10 grams of the two monomers in various ratios ranging between 90:10 and 25:75 trans-piperylene:isoprene.
  • the monomers then were copolymerized using the experimental procedure outlined in Example I.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
US05/893,725 1978-04-05 1978-04-05 Polymerization and copolymerization of trans-piperylene and isoprene Expired - Lifetime US4148983A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US05/893,725 US4148983A (en) 1978-04-05 1978-04-05 Polymerization and copolymerization of trans-piperylene and isoprene
CA000322362A CA1120911A (fr) 1978-04-05 1979-02-27 Polymerisation et copolymerisation du trans-piperylene et de l'isoprene
GB7907994A GB2018782B (en) 1978-04-05 1979-03-07 (co) polymerization of conjugated diolefins using a chronium-containing catalyst system
DE19792911307 DE2911307A1 (de) 1978-04-05 1979-03-22 Verfahren zur copolymerisation von cis-1,3-pentadien und trans-1,3-piperylen
FR7908264A FR2421916A1 (fr) 1978-04-05 1979-04-02 Procede de polymerisation et copolymerisation de diolefines conjuguees
IT48570/79A IT1116536B (it) 1978-04-05 1979-04-02 Procedimento per la copolimerizzazione di cis-e trans-1,3 pentadiene
BR7902011A BR7902011A (pt) 1978-04-05 1979-04-03 Processo que compreende a copolimerizacao de cis-1,3-pentadieno e processo que compreende a polimerizacao de pelo menos uma diolefina
NL7902612A NL7902612A (nl) 1978-04-05 1979-04-03 Werkwijze voor de copolymerisatie van geconjugeerde alkadieenen met een chroom bevattend katalysatorsysteem.
JP4086579A JPS54135884A (en) 1978-04-05 1979-04-04 Polymerization and copolymerization method

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5306856A (en) * 1991-06-12 1994-04-26 Huels Aktiengesellschaft Method of manufacturing methylidene-group-containing α,ω-unsaturated oligomers from α,ω-diolefins in the presence of organoaluminum compounds as catalysts
EP0994127A1 (fr) * 1998-10-14 2000-04-19 Bridgestone Corporation Méthode pour la préparation de polybutadiène-1,2 syndiotactique au moyen d'un système catalyseur à base de chrome
US6117956A (en) * 1998-06-01 2000-09-12 Bridgestone Corporation Catalyst composition and polymerization process for producing syndiotactic 1,2-polybutadiene
US6160063A (en) * 1999-12-30 2000-12-12 Bridgestone Corporation Iron-based catalyst for producing binary cis-1,4-/1,2-polybutadiene
US6197888B1 (en) 1999-12-30 2001-03-06 Bridgestone Corporation Process for producing blends of syndiotactic 1, 2-polybutadiene and rubbery elastomers with an iron-based catalyst system
US6288183B1 (en) 1999-12-30 2001-09-11 Bridgestone Corporation Catalyst composition and process for controlling the characteristics of conjugated diene polymers
US6291591B1 (en) 2000-04-13 2001-09-18 Bridgestone Corporation Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers with a chromium-based catalyst system
US6303692B1 (en) 2000-04-13 2001-10-16 Bridgestone Corporation Preparation of blends of syndiotactic 1,2-polybutadiene and rubbery elastomers with a molybdenum-based catalyst system
US6320004B1 (en) 2001-04-05 2001-11-20 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition
US6348550B1 (en) 2000-04-13 2002-02-19 Bridgestone Corporation Molybdenum-based catalyst composition and process for controlling the characteristics of conjugated diene polymers
US6372681B1 (en) * 1998-03-09 2002-04-16 Tosoh Corporation Catalyst for olefin polymer production and process for olefin polymer production employing the catalyst
US6399732B2 (en) 1998-10-14 2002-06-04 Bridgestone Corporation Preparation of conjugated diene polymers by using an iron-based catalayst system
US6433237B1 (en) 2001-02-19 2002-08-13 Bridgestone Corporation Iron-based catalyst composition for producing oligomers of conjugated dienes
US6465585B2 (en) 2001-02-19 2002-10-15 Bridgestone Corporation Chromium-based catalyst composition for producing conjugated diene polymers
US6528588B2 (en) 2000-04-13 2003-03-04 Bridgestone Corporation Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers
US6545107B2 (en) 2001-06-08 2003-04-08 Bridgestone Corporation Molydenum-based catalyst composition for producing syndiotactic 1,2-polybutadiene
US6627712B2 (en) 2001-02-19 2003-09-30 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition

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US2825721A (en) * 1953-01-27 1958-03-04 Phillips Petroleum Co Polymers and production thereof
US3114743A (en) * 1954-12-02 1963-12-17 Goodrich Gulf Chem Inc Method of preparing synthetic rubber
GB835752A (en) 1955-07-15 1960-05-25 Montedison Spa Diolefine polymers and process for preparing same
US3429940A (en) * 1967-08-28 1969-02-25 Columbian Carbon Trimethyl cyclododecatriene process
US3754048A (en) * 1971-12-27 1973-08-21 Goodrich Co B F Diene polymerization
US3804913A (en) * 1972-10-12 1974-04-16 Cities Service Co Process improvement for the manufacture of trimethyl cyclododecatriene

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5306856A (en) * 1991-06-12 1994-04-26 Huels Aktiengesellschaft Method of manufacturing methylidene-group-containing α,ω-unsaturated oligomers from α,ω-diolefins in the presence of organoaluminum compounds as catalysts
US6372681B1 (en) * 1998-03-09 2002-04-16 Tosoh Corporation Catalyst for olefin polymer production and process for olefin polymer production employing the catalyst
AU738987B2 (en) * 1998-06-01 2001-10-04 Bridgestone Corporation Catalyst composition and polymerization process for producing syndiotactic 1,2-polybutadiene
US6117956A (en) * 1998-06-01 2000-09-12 Bridgestone Corporation Catalyst composition and polymerization process for producing syndiotactic 1,2-polybutadiene
EP0994127A1 (fr) * 1998-10-14 2000-04-19 Bridgestone Corporation Méthode pour la préparation de polybutadiène-1,2 syndiotactique au moyen d'un système catalyseur à base de chrome
US6399732B2 (en) 1998-10-14 2002-06-04 Bridgestone Corporation Preparation of conjugated diene polymers by using an iron-based catalayst system
US6197888B1 (en) 1999-12-30 2001-03-06 Bridgestone Corporation Process for producing blends of syndiotactic 1, 2-polybutadiene and rubbery elastomers with an iron-based catalyst system
US6331594B2 (en) 1999-12-30 2001-12-18 Bridgestone Corporation Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers with an iron-based catalyst system
US6288183B1 (en) 1999-12-30 2001-09-11 Bridgestone Corporation Catalyst composition and process for controlling the characteristics of conjugated diene polymers
US6160063A (en) * 1999-12-30 2000-12-12 Bridgestone Corporation Iron-based catalyst for producing binary cis-1,4-/1,2-polybutadiene
US6291591B1 (en) 2000-04-13 2001-09-18 Bridgestone Corporation Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers with a chromium-based catalyst system
US6303692B1 (en) 2000-04-13 2001-10-16 Bridgestone Corporation Preparation of blends of syndiotactic 1,2-polybutadiene and rubbery elastomers with a molybdenum-based catalyst system
US6348550B1 (en) 2000-04-13 2002-02-19 Bridgestone Corporation Molybdenum-based catalyst composition and process for controlling the characteristics of conjugated diene polymers
US6528588B2 (en) 2000-04-13 2003-03-04 Bridgestone Corporation Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers
US6433237B1 (en) 2001-02-19 2002-08-13 Bridgestone Corporation Iron-based catalyst composition for producing oligomers of conjugated dienes
US6465585B2 (en) 2001-02-19 2002-10-15 Bridgestone Corporation Chromium-based catalyst composition for producing conjugated diene polymers
US6627712B2 (en) 2001-02-19 2003-09-30 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition
US6320004B1 (en) 2001-04-05 2001-11-20 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition
US6545107B2 (en) 2001-06-08 2003-04-08 Bridgestone Corporation Molydenum-based catalyst composition for producing syndiotactic 1,2-polybutadiene

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